Trimethylolalkane esters and method of treating textile filaments therewith



United States Patent Office 3,464,922 Patented Sept. 2, 1969 3,464,922TRIMETHYLOLALKANE ESTERS AND METH- OD OF TREATING TEXTILE FILAMENTSTHEREWITH William F. Bernholz, Wayne, and Thomas C. Cox, Boonton, N.J.,assignors to Drew Chemical Corporation, New York, N.Y., a corporation ofDelaware N Drawing. Filed Dec. 10, 1965, Ser. No. 513,070 Int. Cl. D06m13/20 U.S. Cl. 2528.6 20 Claims ABSTRACT OF THE DISCLOSURE Thisdisclosure is directed to trimethylolalkane esters, to textile finishestherefrom, and to the method of applying these finishes to syntheticlinear organic polymer filaments. For example, the trimethylolalkanemixed triester of capric, lauric, myristic, and palmitic acids in anaqueous emulsion may be used as a finish for polyamide yarns.

The present invention relates to finishes for filaments of syntheticlinear organic polymers. The present invention further relates to amethod of applying these finishes to synthetic linear organic polymerfilaments.

Synthetic linear organic polymers, for example, polyamides such as nylonare commonly formed into filaments by the process of melt-spinning, andthe resultant filaments are drawn in the solid state in order to developa high degree of tenacity so that they become suitable for textilepurposes. To facilitate the drawing of the filaments and other textilesprocessing to which they may be submitted, it is necessary to apply afinish to the newly melt-spun material, in order to reduce frictionduring passage of the filaments over surfaces in textile machinery. Suchreduction in coefficient of friction between the fiberto-metal surfacesprevents filament abrasion. The finishes must be capable of lubricatingthe filaments so that they do not break during drawing. In the case ofmulti-filament yarn it is furthermore necessary that the finish providesome degree of balanced cohesion between the constituent filaments ofthe yarn. This cohesion is particularly important in flat warp knitting.It is also very desirable that the finish have a high degree ofoxidation resistance, including resistance of both discoloration andformation of insoluble resinous or polymeric compounds. It is furtherdesirable that the finish exhibit high temperature stability andresistance to smoke generation at temperatures encountered during theprocessing of the synthetic linear organic polymer filaments. Theselatter characteristics are particularly applicable to the hot stretchingoperation used during the production of synthetic linear organicpolymers.

It is an object of the present invention to provide finishes forfilaments of synthetic linear organic polymers.

Another object of the present invention is to'provide finishes forfilaments of synthetic linear organic polymers to reduce the coefficientof friction between fiber-to-metal surfaces.

A further object of the present invention is to provide finishes forfilaments of synthetic linear organic polymers to provide balancedcohesion between the fiber-tofiber surfaces.

A still further object of the present invention is to provide finishesfor filaments of synthetic linear organic polymers that are resistant tooxidation, discoloration, and the formation of insoluble resinous orextraneous polymeric materials.

A still further object of the present invention is to provide finishesfor filaments of synthetic linear organic polymers that exhibit thermalstability and resistance to smoke generation, particularly duringhot-stretch processing to orient the polymer in order to obtain maximumuniformity of tensile strength, such as in nylon tire cord production.

A still further object of the present invention is to provide a methodof applying finishes to filaments of synthetic linear organic polymers.

A further object is to provide an improvement in the manufacture offilaments and yarns of synthetic linear organic polymers by treatingsuch filaments or yarns with a finishing composition having lubricityand resistance to oxidation and discoloration at elevated temperatures.

Accordingly, the present invention consists of finishes for filaments ofsynthetic linear organic polymers which are trimethylolalkane estersrepresented by the general formula:

wherein R is an alkyl group containing from 1 to 4 carbon atoms and R,R, and R' are saturated and/or unsaturated acyl radicals containing from2 to 24 carbon atoms. Both simple trimethylolalkane esters, i.e. thosewhere R, R", and R are the same acyl radical and mixed trimethylolalkaneesters are contemplated in the present invention. Preferably thetrimethylolalkane ester should contain at least two different acylradicals wherein at least one radical contains from 2 to 12 saturatedcarbon atoms and at least one radical contains from 14 to 24 saturatedand/ or unsaturated carbon atoms. While it is preferred that the acylradical be derived from saturated and unsaturated straight chain acids,acyl groups derived from branched chain acids such as the neo-acids, forexample .neoheptanoic acid, neononanoic acid, etc., or isoacids such asisostearic acid, are contemplated.

The methods of preparation of the trimethylolalkane esters are known inthe art of esterification. In general, three moles of the acid or acidmixture is reacted, generally with refluxing, with one mol of thetrimethylolalkane in the presence of toluene or other suitable diluent.The uncatalyzed reaction occurs at temperatures ranging from C. to 265C. and over a period of time ranging from 4 to 12 hours until thetheoretical amount of Water of reaction is released and collected. Thereaction may also be catalyzed with, for instance, an aromatic sulfonicacid such as para toluene sulfonic acid, which will substantially reducethe reaction time. The resultant substantially completely esterifiedtrimethylolalkane ester is then recovered, illustratively by strippingunder vacuum, to obtain the ester product having a low free fatty acidvalue.

Suitable illustrative esters coming within the scope of this inventionare trimethylolethane monoacetate dioleate, trimethylolethane monooleatediacetate, trimethylolpropane triisopentanoate, trimethylolethanetriheptanoate, trimethylolpropane heptanoate, trimethylolethanetripelargonate, trimethylolpropane monocaprylate dicaprate,trimethylolethane dicaprylate monocaprate, trimethylolpropanedicaprylate monocaprate, trimethylolethane neoheptanoate,trimethylolethane neononanoate, and the trimethylolpropane mixed esterof lauric and myristic acids. Further examples are the trimethylolethaneand trimethylolpropane triesters, monoacetate diesters, diacetatemonoesters, diisopentanoate monoesters, monoisopentanoate diesters andmonooleate diesters of the following mixed acids in the statedproportions: about 0-10% capric, about 45-75% lauric, about 5-35%myristic and about 020'% palmitic, or desirably, about 0.34% capric,about 50-70% lauric, about 1025% myristic and about 2-16% palmitic. Anadvantageous mixture of acids comprises about 15% capric, about 53-68%lauric, about 1525% myristic and about 3- palmitic.

The finishes may be applied neat to the filaments of the syntheticlinear organic polymers or dissolved in a solvent or as an aqueousemulsion. In general, the method of application is governed by thepercentage of lubricant, type of polymer, type of process, and the typeof equipment available. The mode of application of the finish to theyarn filaments will depend upon the system which is most suited to themethod of synthetic linear polymer processing. Generally, from 0.5 tofinish by weight of the organic polymer is applied thereto. The finishmay be further applied by internal addition to the organic polymer priorto melt spinning of it with subsequent bleeding to the surface.

In preparing an aqueous emulsion containing the finish, any singularsurfactant or combination of surfactants compatible with the finish andcapable of forming a stable emulsion may be utilized. A sample aqueousemulsion is prepared, using conventional procedures, with the followingproportional ingredients:

15 parts Other suitable surfactants are sulfated trioleate ethoxylatedtridecyl alcohol, polyglycerol esters such as decaglycerol tetraoleate,triethanolamine oleate, ethoxylated nonyl phenol, etc. Generally theaqueous emulsion con tains from 1 to 25% nonaqueous solids which in turnconsists of from 50 to 80 parts of the finish and 50 to parts of theemulsifier.

Suitable solvents for use in applying the finishes include the lowermolecular weight alkanols, such as ethanol or propanol; ketones such asacetone; and hydrocarbons such as toluene or petroleum ether. Thesolvent selected should be compatible with the polymer to which is isapplied.

Other ingredients such as antistatic agents, emulsification aids,lubricant aids to impart cohesion properties, etc. may be used inconjunction with the finishes of the present invention provided they donot seriously affect or alter the characteristics of said finishes.

The invention includes the application of the finishes to the filamentsand the filaments which have been so treated. The term filaments is tobe understood as including monofilamentous and multifiamentous yarnwhether twisted or not.

The synthetic linear organic polymers include polyamides such aspolyhexamethylene sebacamide, poly- Kappa-aminoundecanoic acid,poly-epsilon-caprolactam, etc.; acrylic polymers made largely fromacrylonitrile; polyolefins such as polymethylene, polyethylene,polypropylene, etc.; polyesters such as polyethylene terephthalate, andother polyesters formed by reaction of a dihydric alcohol and a diacid,etc.; and polyureas such as polyhexamethylene urea, etc.

The following examples further describe the invention.

Example 1 A trimethylolethane mixed triester (TME) made from a mixtureof acids comprising 4% capric, 57% lauric, 32% myristic, and 7% palmiticwas tested for its resistance to oxidation; discoloration, and theformation of insoluble resinous or extraneous polymerized material incomparison to a commercial rearranged vegetable oil textile fiberfinish. Both the mixed esters of the present invention and the controlfinish were subjected to strong oxidizing conditions, namely, constantheat for 24 hours at a temperature of about 180 C. with continuous airsweep of 2 liters per minute (1 liter per kilogram of material). Theseconditions were regarded as simulating in situ plant processingconditions. Changes in saponification value (A.O.C.S. method Cd 3-25)and viscosity at F. (Saybolt Universal Seconds) are indicative of theformation of resinous or polymerized material. Hydroxyl value (A.O.C.S.method Cd 440) and free fatty acid (A.O.C.S. method Ca 5a-40) areindicative of hydrolytic thermal stability. The color measurements aremade using the Lovibond color scale.

B More ox idatiou After oxidation TME ME Finish CRVO 1 ester CRVO 1ester Test results:

FFA (free fatty acids) H 0. 01 0.035 5. 8 4. 5 Hydroxyl No 0 1.0 33. 426. 5 Saponification value 257. l 242. 8 283. 4 289. 2 Viscosity e 350285 Color 6.0/1.0 2. 0/0. 2 16. O/4. 0 8. 0/1. 5

1 CRVO stands for Commercial Rearranged Vegetable Oil.

The foregoing results clearly illustrate the high thermal stability,greater resistance to discoloration and low amount of resinous orpolymerized materials exhibited by the trimethylolethane mixed triesteras compared to the commercial rearranged vegetable oil finish.

Example 2 The fiber-to-fiber friction characteristics of 840/ 140 denierpolyamide yarn were tested by the solvent application of 1%trimethylolalkane ester by weight of the yarn in comparison to a controlyarn from which the finish had been scoured. Conditions of test were atemperature of 72 F. and a relative humidity of 25%. The attenuation wasas follows:

Turn of yarn 1 /2 (540) times. Pendent weight 20 gms.

Chart speed 2.5 mm./sec. Speed of yarn 1.07 mm./sec.

' Both the coefiicient of friction expressed in gms. and millimetersbetween slipstick were evaluated as follows:

Cocil'. of Mm. between Finish friction slip-stick Control (scoured) 85 Ol Trimethylolethane triester 65 2. 5 Trimethylolethane oleate este 65 2.5

l Trirnethylolethane mixed triester of the following acids in the Statedproportions: 2% eapric, 65% lauric, 25% myristic, and 8% palmitic.

2 50 parts of the above triester rearranged with 50 parts oftrimethylolethane triolate.

Example 3 The fiber-to-rnetal friction characteristics of a 840/140denier polyamide yarn which had been treated with a 1% solventapplication of the trimethylolalkane ester, versus such characteristicsof a scoured (without finish) yarn. Conditions of the test were asfollows:

Temperature F 72 Relative humidity percent 25 Speed of yarn m./min 100Total weight of pulley gms 100 Radians 5 The differential friction ingrams, which is indicative of greater friction as it increases, isexpressed in grams:

Finish: Differential friction None (scoured control) 200Trimethylolethane triester of Example I 110 The foregoing resultsindicate the superior fiber-tO-metal lubricity of the trimethylolalkaneester.

Example 4 The smoke, fire, and flash characteristics (A.O.C.S. methodCc-9a-48) of the trimethylolethane mixed triester of Example I wascompared to those of a commercial rearranged vegetable oil filamentfinish. The results which are as follows illustrates the minimizedtendency of trimethylolethane ester to cause smoke formation.

Smoke, Flash, Fire,

Finish F. F F.

Commercial rearranged vegetable oil 400 570 610 Trimethyiolethanetriester of Example 1 450 575 635 om-on' n- -oni-on" Hr-OR' wherein R isan alkyl group containing from 1 to 4 carbon atoms and R, R, and R areselected from the class consisting of saturated and unsaturated acylradicals containing from 2 to about 24 carbon atoms per radical, andmixtures thereof wherein at least one of the chemical moieties R, R",and R consist of an acyl radical containing 2 to 12 saturated carbonatoms and at least another of the said chemical moieties consist of atleast one acyl radical containing 14 to 24 saturated or unsaturatedcarbon atoms.

2. The trimethylolalkane ester of claim 1 comprising predominantlytrimethylolethane monoacetate dioleate.

3. The trimethylolalkane ester of claim 1 comprising predominantlytrimethylolethane monooleate diacetate.

4. The trimethylolalkane esters of claim 1 comprising predominantlytrimethylolalkane mixed triester of mixed acids, said mixed acidscomprising about 10% capric, about 45-75% lauric, about 35% myristic,and about 020% palmitic.

5. The trimethylolalkane esters of claim 1 consisting essentially of thetrimethylolethane monooleate diester of mixed acids, said mixed acidscomprising about 0-10% capric, 45-75% lauric, 5-35% myristic and 015%palmitic.

6. The trimethylolalkane esters of claim 1 comprising predominantlytrimethylolalkane mixed triester of mixed acids, said mixed acidscomprising about 0.3-7% capric, about 50-70% lauric, about -25% myristicand about 2-16% palmitic.

7. The trimethylolalkane esters of claim 1 comprising predominantlytrimethylolalkane mixed triester of mixed acids, said mixed acidscomprising about 15% capric, about 53-68% lauric, about -25% myristicand about 310% palmitic.

8. A textile finish comprising an aqueous emulsion of thetrimethylolalkane esters of claim 1.

9. A textile finish composition comprising the trimethylolalkane estersof claim 1 and a solvent for said esters.

10. The method of finishing synthetic organic polymers which comprisesadding the esters of claim 1 in a solvent to synthetic organic polymers,wherein the amount of said esters used is in the range of from 0.5-

5 15% based on the Weight of synthetic organic polymers.

11. The method of finishing filaments which comprises adding the estersof claim 1 to synthetic organic polymers and forming filaments therefromwherein the amount of said esters used is in the range from 05-15% basedon the weight of said filaments.

12. The trimethylolalkane esters of claim 4 comprising predominantly thetrimethylolethane monoacetate diester of said mixed acids.

13. A textile finish comprising an aqueous emulsion of thetrimethylolalkane esters of claim 4.

14. A method of treating filaments of synthetic linear organic polymerscomprising adding to said filaments a finish comprising at least onetrimethylolalkane ester represented by the general formula:

wherein R is an alkyl group containing from 1 to 4 carbon atoms and R,R, and R' are selected from the class consisting of saturated andunsaturated acyl radicals containing from 2 to about 24 carbon atoms perradical, 3 and mixtures thereof, wherein at least one of the chemicalmoieties R, R and R consists of an acyl radical containing 14-24saturated or unsaturated carbon atoms, wherein the amount of said one ormore esters used is in the range of from about 0.515% based on theweight of said filaments.

15. A method according to claim 14 wherein said finish consistsessentially of trimethylolethane triheptanoate.

16. A method according to claim 14 wherein said finish consistsessentially of trimethylolethane monoacetate dioleate.

17. A method according to claim 14 wherein said finish consistsessentially of trimethylolethane mixed triester of mixed acids, saidmixed acids comprising about 0.3- 10% capric, about 45-75% lauric, about5-35% myristic and about 115% palmitic.

18. A method according to claim 14 wherein said finish comprisestrimethylolethane monoacetate diester of the following acids in thestated proportions: 010% C capric, 4575% C lauric, 5-35% C myristic, 0-15 C palmitic.

19. A method according to claim 14 wherein said finish comprisestrimethylolethane monooleate diester of the following acids in thestated proportions: 0-10% capric, 4575% lauric, 535% myristic, 0-15palmitic.

20. The method of claim 14 wherein said one or more esters are added inthe form of an aqueous emulsion.

References Cited UNITED STATES PATENTS 2,917,410 12/1959 Vitalis1l7--138.8 2,991,297 7/1961 Cooley et al 260410.6 3,000,917 9/1961Babayan 260-4106 X 3,160,511 12/1964 Skeen et a1. 1l7-139.5X 3,282,97111/1966 Metro et a1. 260410.6

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner 0 7U.S. Cl. X.R.

